CN109627446A - A kind of preparation facilities of polysilazane and preparation method thereof - Google Patents
A kind of preparation facilities of polysilazane and preparation method thereof Download PDFInfo
- Publication number
- CN109627446A CN109627446A CN201811641247.6A CN201811641247A CN109627446A CN 109627446 A CN109627446 A CN 109627446A CN 201811641247 A CN201811641247 A CN 201811641247A CN 109627446 A CN109627446 A CN 109627446A
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- China
- Prior art keywords
- double
- tube type
- product
- type reactor
- polysilazane
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- 229920001709 polysilazane Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 121
- 239000000047 product Substances 0.000 claims abstract description 95
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000012043 crude product Substances 0.000 claims abstract description 66
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 239000006227 byproduct Substances 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims description 59
- 239000010410 layer Substances 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 39
- 238000012546 transfer Methods 0.000 claims description 27
- 239000002826 coolant Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000011229 interlayer Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- 238000005194 fractionation Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 3
- 230000004044 response Effects 0.000 description 7
- 238000010924 continuous production Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 3
- 239000005046 Chlorosilane Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
- B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
Abstract
The invention belongs to chemical fields, and in particular to a kind of preparation facilities of polysilazane and preparation method thereof.Described device includes double-tube type reactor, raw material liquid supplying device, gas feed unit, cooling device, product separator, byproduct collection device, product fractionating device, solvent collection device and polysilazane collection device；Crude product after reaction enters product separator by tubular reactor lower ending opening, while by-product is separated, unreacted high-purity ammonia is transmitted back to reactor cycles with mixed liquor and is reacted, making full use of for raw material is realized, the waste for greatly reducing raw material, improves conversion ratio；Can in time, efficiently separate by-product in preparation process, avoid tank reactor and generate the shortcomings that a large amount of by-products hinder ammonias and raw material liq to contact, shorten the reaction time；Improve production efficiency.
Description
Technical field
The invention belongs to chemical fields, and in particular to a kind of preparation facilities of polysilazane and preparation method thereof.
Background technique
Polysilazane chemical reactivity with higher, it is to prepare silicon nitride and silicon-carbon ceramics precursor that heat resisting temperature is high
The important source material of body, but in the polysilazane of ammonia ammonolysis chlorosilane synthesis at present, do not there is continuous production device on a large scale；
Raw material high-purity ammon solid/liquid/gas reactions are excessively more, and direct emission not only wastes, and pollute environment；By-product on reaction rate influence compared with
Greatly, the problem that by-product hinders reaction to carry out is difficult to solve.
Summary of the invention
In view of this, the object of the present invention is to provide it is a kind of can with the preparation facilities of continuous production polysilazane and its
Preparation method substantially increases the utilization rate of raw material and the yield of product, and pipe reaction in such a way that double raw materials are bicirculating
Device can constantly separate by-product and raw material, product with product separator, improve reaction efficiency.
To achieve the above object, technical scheme is as follows.
A kind of preparation facilities of polysilazane, described device include quartzy double-tube type reactor, raw material liquid supplying device,
Gas feed unit, cooling device, product separator, byproduct collection device, product fractionating device, solvent collection device and poly-
Silazane collection device；
Wherein, raw material liquid supplying device provides material liquid to the top of double-tube type reactor, and gas feed unit is to double
The top of layer tubular reactor provides gas, and cooling device provides coolant liquid, product separation to the interlayer of double-tube type reactor
Device collects the crude product of double-tube type reactor bottom, and unreacted gas circulation conveying is to double-tube type reactor in crude product
Top, Solid Conveying and Melting in crude product to byproduct collection device；
The liquid delivery tube road of described device is equipped with thief hatch, for acquiring the liquid in crude product, sample liquid warp
When detection polysilazane meets requirement, then collects to product fractionating device, be otherwise recycled to the upper of double-tube type reactor
Portion；
To the solvent collection device at top, polysilazane is delivered to solvent delivery after liquid fractionation in product fractionating device
The polysilazane collection device of bottom.
Further, gas feed mouth and recyclegas feed inlet, double-tube type are provided at the top of double-tube type reactor
The two sides on reactor top are symmetrically provided with material liquid feed inlet and recycle feed liquid feed inlet, and the bottom of double-tube type reactor is opened
There is products export, the outer layer upper and lower ends of double-tube type reactor have coolant liquid feed inlet and coolant liquid discharge port；
Raw material liquid supplying device is delivered to the material liquid feed inlet of double-tube type reactor through feedstock transportation pipeline, for
Liquid charging stock is provided in double-tube type reactor；
Gas feed unit is delivered to the gas feed mouth of double-tube type reactor through gas transfer pipeline, is used for bilayer
Gas needed for reacting is provided in tubular reactor；
Cooling device is connect with the coolant liquid feed inlet of double-tube type reactor and coolant liquid discharge port respectively, is used for double
Coolant liquid is provided in the interlayer of layer tubular reactor；
Product separator is connect with the outlet for product of double-tube type reactor, for collecting the crude product after reacting；It produces
Ammonia discharge port is provided at the top of product separator, the gas in crude product is delivered to double-tube type reactor through gas circulation line
Recyclegas feed inlet；The side of product separator is provided with by-product discharge port, and discharge outlet is equipped with sieve plate, product separator
Inside be equipped with spiral conveyor rod, the bottom of spiral conveyor rod is equipped with filter plate；Crude product is delivered to by-product by spiral conveyor rod
Discharge port, the solid in crude product squeeze into byproduct collection device through sieve plate, and the bottom of product separator is provided with outlet for product；
Liquid in crude product exports after filter plate filters out and is flowed out by outlet for product through product transfer pipeline, by acquisition port collection liquid
Body sample, meets the requirements, and is delivered to fractionating device, is then delivered to recycle feed liquid feed inlet if it does not meet the requirements；
The top of product fractionating device is equipped with solvent discharge port, and the bottom of product fractionating device discharges equipped with polysilazane
Mouthful, after the liquid fractionation in crude product, solvent is flowed out by solvent discharge port and is delivered to solvent collection device through cooling tube cooling；
Polysilazane is delivered to polysilazane collection device after being flowed out by polysilazane discharge port；
The gas circulating tube road of described device is equipped with emptying pipeline, for emptying the air in double-tube type reactor.
Further, the transfer pipeline of described device is equipped with valve, delivery pump, flowmeter, temperature sensor and temperature
Detector, delivery pump, flowmeter, temperature sensor and controller connect, and the delivery pump includes on material liquid transfer pipeline
The product delivery pump on circulation ammonia delivery pump and product transfer pipeline on material liquid delivery pump, circulation ammonia transfer pipeline, it is described
Flowmeter includes the fluid flowmeter and gas flowmeter being set on pipeline；The valve includes the non-return being set on pipeline
Valve, shut-off valve and pressure reducing valve, check-valves is in the open state to be prevented from flowing backwards, and shut-off valve is in normally open when use, is only tieed up
It is in close state when repairing, pressure reducing valve is used to control the gas pressure inputted by gas feed unit；
The junction of the double-tube type reactor and product separator is equipped with crude product outlet valve, products export when use
Valve is in normally open, and only product separator goes wrong or inspecting state can just be opened, and prevents the clout in reactor
Outflow.
Further, multilayer circular ring type isocon is equipped in the top interlayer of the double-tube type reactor, isocon
Both ends are provided with isocon feed inlet and isocon recycle feed mouth respectively, isocon feed inlet and double-tube type reactor top
The connection of material liquid feed inlet, isocon recycle feed mouth are connect with the recycle feed liquid feed inlet on double-tube type reactor top,
Multiple isocon feed inlets are provided on every layer of isocon, the internal layer of double-tube type reactor is provided with multiple and isocon feed inlet and connects
The connector connect.
Further, the isocon is horizontally disposed three layers of circular ring type structure, is uniformly provided with 4~16 on every layer of annulus
Horizontal plane is divided into 12~48 equal parts by a feed inlet, feed inlet interval on three layers of annulus.
Further, pressure sensor is respectively equipped at the top of the top of the double-tube type reactor and product separator
With relief valve assembly.
Further, the filter-plate structure includes two layers of porous hard steel plate and 10~30 layers of cotton being clipped between steel plate
Fiber or non-woven fabrics.
Further, the internal diameter of the double-tube type reactor is 100~1000mm, and outer diameter is 140mm~1200mm, high
Degree is 1000mm~5000mm.
A method of polysilazane being prepared using device of the present invention, the method comprises the following steps:
Step S1: from gas feed unit into double-tube type reactor supplying nitrogen, device is purged, device is made
Under nitrogen environment, excluding air moisture influences；
Step S2: -20~-35 DEG C of coolant liquid is conveyed into the interlayer of double-tube type reactor from cooling device；
Step S3: dimethyldichlorosilane is mixed with solvent according to the volume ratio of 1:1~50, material liquid supply dress is added
In setting, and be delivered to the top of double-tube type reactor, at the same from gas feed unit into double-tube type reactor delivering ammonia
Gas；The flow velocity of ammonia and material liquid is controlled, reactor pressure is kept to maintain normal pressure, reaction temperature is made to be less than or equal to 5 DEG C；
Step S4: the crude product after reaction is flowed into product separator by double-tube type reactor bottom, will be in crude product
Unreacted ammonia recycle is delivered to the top of double-tube type reactor, and the Solid Conveying and Melting in crude product to by-product is collected and is filled
It sets；After liquid output in crude product, by the fluid sample in thief hatch acquisition crude product, the polysilazane in test sample is
It is no to meet requirement, next step operation is carried out if meeting；The top of double-tube type reactor is recycled to if not meeting, weight
Multiple step S3, the raw material flow velocity of control ammonia, ammonia recycle and circulating liquid, keeps reactor pressure to maintain normal pressure,
Reaction temperature is set to be less than or equal to 5 DEG C；Until meeting requirement carries out next step operation；
Step S6: the liquid for meeting requirement is delivered in product fractionating device, after fractionation, by solvent collection device
The solvent for collecting recoverable is collected the polysilazane for meeting requirement by polysilazane collection device.
Preferably, the volume ratio of the dimethyldichlorosilane and solvent is 1:10~20.
Preferably, the solvent is one or more of n-hexane, hexamethylene, benzene, toluene, tetrahydrofuran and butyl ether.
The utility model has the advantages that crude product after reaction enters production by tubular reactor lower ending opening in device of the present invention
Unreacted high-purity ammonia while separating by-product, is transmitted back to reactor cycles with mixed liquor and reacted by object separator, real
Making full use of for raw material is showed, has greatly reduced the waste of raw material, improve conversion ratio；Can in time, efficiently separate and prepared
By-product in journey avoids tank reactor and generates the shortcomings that a large amount of by-products hinder ammonia and raw material liq to contact, shortens
Reaction time；So that batch production is become continuous production, improves production efficiency.
In the method for the invention, raw material dimethyldichlorosilane and methyl hydrogen dichlorosilane or perhydro dichlorosilane phase
Than property is relatively stable, is liquid in room temperature, ensure that controllable with ammonia reaction rate.And there is only ammonias one in gas phase
Kind substance, it is therefore prevented that methyl hydrogen dichlorosilane or perhydro chlorosilane generate gas phase in raw material liquid supplying device, deposit in pipeline
Or the problem of corrosion, ammonia is recycled.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of device of the present invention.
Fig. 2 is the top view of isocon in device of the present invention.
Fig. 3 is the main view of isocon in device of the present invention.
Wherein, 1- raw material liquid supplying device；2- material liquid delivery pump；3- check-valves；4- shut-off valve；5- fluid flowmeter；
6- gas transfer pipeline；7- isocon；8- double-tube type reactor；9- temperature detector；10- fixes bracket；11- products export
Valve；12- product separator；13- byproduct collection device；14- recycles ammonia delivery pump；15- gas circulation line；16- product is defeated
Send pump；17- thief hatch；18- product transfer pipeline；19- product fractionating device；20- cooling tube；21- solvent collection device；22-
Polysilazane collection device；23- gas flowmeter；24- pressure sensor and relief valve assembly；25- cooling device；26- raw material
Liquid transfer pipeline；27- pressure reducing valve；28- controller；29- spiral conveyor rod；30- sieve plate；31- filter plate；32- empties pipeline；61-
Isocon feed inlet；62- isocon recycle feed mouth；The upper layer 63- isocon feed inlet；The middle layer 64- isocon feed inlet；65-
Lower layer's isocon feed inlet.
Specific embodiment
The present invention is further described with reference to the accompanying drawings and detailed description.
As shown in Figure 1, a kind of preparation facilities of polysilazane, described device includes quartzy double-tube type reactor 8, raw material
Liquid supplying device 1, gas feed unit, cooling device 25, product separator 12, byproduct collection device 13, product fractionation dress
Set 19, solvent collection device 21 and polysilazane collection device 22；
Wherein, raw material liquid supplying device 1 to the top of double-tube type reactor 8 provide material liquid, gas feed unit to
The top of double-tube type reactor 8 provides gas, and cooling device 25 provides coolant liquid to the interlayer of double-tube type reactor 8, produces
Product separator 12 collects the crude product of 8 bottom of double-tube type reactor, and unreacted gas circulation conveying is to bilayer in crude product
The top of tubular reactor 8, Solid Conveying and Melting in crude product to byproduct collection device 13；Liquid in crude product is delivered to production
Product fractionating device 19 or circulation conveying are to the top of double-tube type reactor 8；
The liquid delivery tube road of described device is equipped with thief hatch 17, for acquiring the liquid in crude product, sample liquid
When meeting requirement through detecting polysilazane, then collects to product fractionating device 19, be otherwise recycled to double-tube type reactor 8
Top；
For solvent delivery to the solvent collection device 21 at top, polysilazane is defeated after liquid fractionation in product fractionating device 19
It send to the polysilazane collection device 22 of bottom.
The top of double-tube type reactor 8 is provided with gas feed mouth and recyclegas feed inlet, on double-tube type reactor 8
The two sides in portion are symmetrically provided with material liquid feed inlet and recycle feed liquid feed inlet, and the bottom of double-tube type reactor 8 is provided with product
Outlet, the outer layer upper and lower ends of double-tube type reactor 8 have coolant liquid feed inlet and coolant liquid discharge port；
Raw material liquid supplying device 1 is delivered to the material liquid feed inlet of double-tube type reactor through feedstock transportation pipeline, is used for
Liquid charging stock is provided into double-tube type reactor；
Gas feed unit is delivered to the gas feed mouth of double-tube type reactor 8 through gas transfer pipeline 6, is used for double
Gas needed for reacting is provided in layer tubular reactor 8；
Cooling device 25 is connect with the coolant liquid feed inlet of double-tube type reactor 8 and coolant liquid discharge port respectively, is used for
Coolant liquid is provided into the interlayer of double-tube type reactor 8；
Product separator 12 is connect with the outlet for product of double-tube type reactor 8, for collecting the crude product after reacting；
The top of product separator 12 is provided with ammonia discharge port, and the gas in crude product is delivered to double-tube type through gas circulation line 15
The recyclegas feed inlet of reactor 8；The side of product separator 12 is provided with by-product discharge port, and discharge outlet is equipped with sieve plate
30, the inside of product separator 12 is equipped with spiral conveyor rod 29, and the bottom of spiral conveyor rod 29 is equipped with filter plate 31；Crude product is by spiral shell
Rotation conveying lever 29 is delivered to by-product discharge port, and the solid in crude product squeezes into byproduct collection device 13, product through sieve plate 30
The bottom of separator 12 is provided with outlet for product；Liquid in crude product passes through after filter plate 31 filters out and is flowed out by outlet for product
Product transfer pipeline 18 exports, and acquires fluid sample by acquisition port, meets the requirements, is delivered to fractionating device, if it does not meet the requirements
Then it is delivered to recycle feed liquid feed inlet；
The top of product fractionating device 19 is equipped with solvent discharge port, and the bottom of product fractionating device 19 goes out equipped with polysilazane
Material mouth, after the liquid fractionation in crude product, solvent is flowed out by solvent discharge port and is collected through the cooling solvent that is delivered to of cooling tube 20
Device 21；Polysilazane is delivered to polysilazane collection device 22 after being flowed out by polysilazane discharge port；
The gas circulating tube road of described device is equipped with emptying pipeline 32, for emptying the sky in double-tube type reactor
Gas.
The transfer pipeline of described device is equipped with valve, delivery pump, flowmeter, temperature sensor and temperature detector 9, defeated
Pump, flowmeter, temperature sensor and controller 28 is sent to connect, the delivery pump includes the material liquid on material liquid transfer pipeline 26
The product delivery pump 16 on circulation ammonia delivery pump 14 and product transfer pipeline 18 on delivery pump 2, circulation ammonia transfer pipeline 15, institute
Stating flowmeter includes the fluid flowmeter 5 and gas flowmeter 23 being set on pipeline；The valve includes being set on pipeline
Check-valves 3, shut-off valve 4 and pressure reducing valve 27, check-valves 3 is in the open state to be prevented from flowing backwards, and shut-off valve 4 is in normal when use
Open state is in close state when only maintenance, and pressure reducing valve 27 is used to control the gas pressure inputted by gas feed unit.
The junction of the double-tube type reactor 8 and product separator 12 is equipped with crude product outlet valve 11, products export valve when use
11 are in normally open, and only product separator 12 goes wrong or inspecting state can just be opened, and prevents remaining in reactor
Stream goes out.
Further, multilayer circular ring type isocon 7, isocon 7 are equipped in the top interlayer of the double-tube type reactor 8
Both ends be provided with isocon feed inlet 61 and isocon recycle feed mouth 62 respectively, isocon feed inlet 61 is reacted with double-tube type
The material liquid feed inlet on 8 top of device connects, the recycle feed liquid of isocon recycle feed mouth 62 and 8 top of double-tube type reactor
Feed inlet connects, and multiple isocon feed inlets are provided on every layer of isocon, and the internal layer of double-tube type reactor 8 is provided with multiple and divides
The connector of flow tube feed inlet connection.
The isocon 7 is horizontally disposed three layers of circular ring type structure, and 4~16 upper layers point are uniformly provided on the annulus of upper layer
Flow tube feed inlet 63 is uniformly provided with 4~16 middle layer isocon feed inlets 64 on the annulus of middle layer, is uniformly provided with 4 on lower layer's annulus
Horizontal plane is divided into 12~48 equal parts by~16 lower layer's isocon feed inlets 65, feed inlet interval on three layers of annulus；Such as
Shown in Fig. 2-3.
The top of the double-tube type reactor 8 and the top of product separator 12 are respectively equipped with pressure sensor and safety
Valve module 24.
31 structure of filter plate include two layers of porous hard steel plate and 10~30 layers of cotton fibre being clipped between steel plate or
Non-woven fabrics.
The internal diameter of the double-tube type reactor 8 is 100~1000mm, and outer diameter is 140mm~1200mm, is highly
1000mm~5000mm.
Embodiment 1
The internal diameter of double-tube type reactor described in the present embodiment 8 is 100mm, outer diameter 140mm, is highly 1200mm.
A kind of use device of the present invention prepares polysilazane, and (400) purity 95%, number-average molecular weight size are
Method, the method comprises the following steps:
Step S1: from gas feed unit into double-tube type reactor 8 supplying nitrogen, device is purged, makes to fill
It sets under nitrogen environment, excluding air moisture etc. influences；
Step S2: cooling device 25 conveys -35 DEG C of glycol-cooled liquid into the interlayer of double-tube type reactor 8；
Step S3: dimethyldichlorosilane is mixed with solvent hexane according to the volume ratio of 1:10, material liquid supply is added
In device 1, and through the upper of material liquid transfer pipeline conveying 26 to double-tube type reactor 8 under the action of material liquid delivery pump 2
The flow velocity in portion, material liquid is 100ml/min, while conveying purity into double-tube type reactor 8 from gas feed unit and being
99.99995 high-purity ammonia, flow velocity 2400ml/min；8 interior reaction temperature of double-tube type reactor is -5 DEG C, and pressure is normal
Pressure；
Step S4: the crude product after reaction is flowed into 12 in product separator by the discharge port of 8 bottom of double-tube type reactor,
Solid in crude product is delivered to byproduct collection device 13 after spiral conveyor rod 29 and sieve plate 30；Liquid in crude product
It is exported under the action of product delivery pump 16 through product transfer pipeline 18, the liquid-like in crude product is acquired at thief hatch 17
Product, the polysilazane in test sample is undesirable；
Step S5: carry out first time circular response, by the ammonia in crude product under the action of recycling ammonia delivery pump 14 with
The top that the flow velocity of 800ml/min is delivered to double-tube type reactor 8 through recycling ammonia transfer pipeline 15, by the liquid in crude product
The top of double-tube type reactor 8 is recycled to through product transfer pipeline 18 with the flow velocity of 500ml/min；The flow velocity of material liquid is
100ml/min, the flow velocity of ammonia are 2400ml/min, and 8 interior reaction temperature of double-tube type reactor is 1 DEG C, and pressure is normal pressure；
Polysilazane in acquisition sample and test sample does not meet requirement；Second of circular response is then carried out, it will
Ammonia in crude product is with the flow velocity circulation conveying of 800ml/min to the top of double-tube type reactor, by the liquid in crude product
Body is recycled to the top of double-tube type reactor with the flow velocity of 100ml/min；The flow velocity of material liquid is 74ml/min, ammonia flow velocity
For 2000ml/min, double-tube type reactor interior reaction temperature is -3 DEG C, and pressure is normal pressure；
Acquisition sample detection sample in polysilazane it is not no meet requirement, then carry out third time circular response, will
Ammonia in crude product is with the flow velocity circulation conveying of 1000ml/min to the top of double-tube type reactor, by the liquid in crude product
Body is recycled to the top of double-tube type reactor with the flow velocity of 174ml/min；The flow velocity of material liquid is 89ml/min, ammonia flow
Speed is 1000ml/min, and double-tube type reactor interior reaction temperature is -5 DEG C, and pressure is normal pressure；
The purity 95.66% of the polysilazane in sample detection sample is acquired, number-average molecular weight 410 carries out in next step
Operation；
Step S6: the liquid for meeting requirement is delivered in product fractionating device 19 through product transfer pipeline 18, point
After evaporating, the solvent of the recoverable after cooling tube 20 is cooling is collected by solvent collection device 21, by polysilazane collection device
22 collect the polysilazane for meeting requirement.
Embodiment 2
The internal diameter of double-tube type reactor described in the present embodiment 8 is 100mm, outer diameter 140mm, is highly 1200mm.
A kind of use device of the present invention prepares polysilazane, and (600) purity 98%, number-average molecular weight size are
Method, the method comprises the following steps:
Step S1: from gas feed unit into double-tube type reactor 8 supplying nitrogen, device is purged, makes to fill
It sets under nitrogen environment, excluding air moisture etc. influences；
Step S2: cooling device 25 conveyed into the interlayer of double-tube type reactor 8-35 DEG C coolant liquid (glycerine with
The mixed solution of water)；
Step S3: dimethyldichlorosilane is mixed with solvents tetrahydrofurane according to the volume ratio of 1:20, material liquid confession is added
To in device 1, and it is delivered to through material liquid transfer pipeline 26 top of double-tube type reactor 8, raw material flow velocity is 100ml/
Min, while high-purity ammonia that purity is 99.99995 is conveyed into double-tube type reactor 8 from gas feed unit, flow velocity is
1400ml/min；8 interior reaction temperature of double-tube type reactor is -1 DEG C, and pressure is normal pressure；
Step S4: the crude product after reaction is flowed into product separator 12 by 8 bottom of double-tube type reactor, by crude product
In Solid Conveying and Melting to byproduct collection device 13；After liquid output in crude product, the fluid sample in crude product, inspection are acquired
Polysilazane in sample is undesirable；
Step S5: first time circular response is carried out, extremely with the flow velocity circulation conveying of 600ml/min by the ammonia in crude product
Liquid in crude product is recycled to double-tube type reactor 8 with the flow velocity of 500ml/min by the top of double-tube type reactor 8
Top；The flow velocity of material liquid is 100ml/min, and the flow velocity of ammonia is 1400ml/min, reaction temperature in double-tube type reactor 8
Degree is -1 DEG C, and pressure is normal pressure；
Polysilazane in acquisition sample and test sample does not meet requirement；Second of circular response is then carried out, it will
Ammonia in crude product is with the flow velocity circulation conveying of 600ml/min to the top of double-tube type reactor 8, by the liquid in crude product
Body is recycled to the top of double-tube type reactor 8 with the flow velocity of 100ml/min；The flow velocity of material liquid is 82ml/min, ammonia flow
Speed is that 8 interior reaction temperature of 1300ml/min double-tube type reactor is -4 DEG C, and pressure is normal pressure；
Acquisition sample detection sample in polysilazane it is not no meet requirement, then carry out third time circular response, will
Ammonia in crude product is with the flow velocity circulation conveying of 750ml/min to the top of double-tube type reactor 8, by the liquid in crude product
Body is recycled to the top of double-tube type reactor 8 with the flow velocity of 182ml/min；The flow velocity of material liquid is 90ml/min, ammonia
Flow velocity is 1000ml/min, and 8 interior reaction temperature of double-tube type reactor is -3 DEG C, and pressure is normal pressure；
The purity 98.1% of the polysilazane in sample detection sample is acquired, number-average molecular weight 636 carries out next step behaviour
Make；
Step S6: the liquid for meeting requirement is delivered in product fractionating device 19 through product transfer pipeline 18, point
After evaporating, the solvent of the recoverable after cooling tube 20 is cooling is collected by solvent collection device 21, by polysilazane collection device
22 collect the polysilazane for meeting requirement.
In conclusion the present invention devises the circular response of raw material liq and gas, the waste of raw material is greatly reduced, is mentioned
High conversion ratio；Can in time, efficiently separate by-product in preparation process, avoid tank reactor and generate a large amount of by-products
The shortcomings that hindering ammonia and raw material liq to contact, shortens the reaction time；So that batch production is become continuous production, improves life
Produce efficiency.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, made any modification, equivalent replacement etc. be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation facilities of polysilazane, it is characterised in that: described device includes double-tube type reactor (8), material liquid
Feedway (1), gas feed unit, cooling device (25), product separator (12), byproduct collection device (13), product
Fractionating device (19), solvent collection device (21) and polysilazane collection device (22)；
Wherein, raw material liquid supplying device (1) to the top of double-tube type reactor (8) provide material liquid, gas feed unit to
The top of double-tube type reactor (8) provides gas, and cooling device (25) provides cooling to the interlayer of double-tube type reactor (8)
Liquid, product separator (12) collect double-tube type reactor 8) crude product of bottom, unreacted gas circulation is defeated in crude product
It send to the top of double-tube type reactor (8), the Solid Conveying and Melting in crude product to byproduct collection device (13)；In crude product
Liquid is delivered to the top of product fractionating device (19) or circulation conveying to double-tube type reactor (8)；
The liquid delivery tube road of described device is equipped with thief hatch (17), for acquiring the liquid in crude product, sample liquid warp
When detection polysilazane meets requirement, then collects to product fractionating device (19), be otherwise recycled to double-tube type reactor
(8) top；
For solvent delivery to the solvent collection device (21) at top, polysilazane is defeated after liquid fractionation in product fractionating device (19)
It send to the polysilazane collection device (22) of bottom.
2. a kind of preparation facilities of polysilazane as described in claim 1, it is characterised in that: double-tube type reactor (8)
Top is provided with gas feed mouth and recyclegas feed inlet, and the two sides on double-tube type reactor (8) top are symmetrically provided with material liquid
Feed inlet and recycle feed liquid feed inlet, the bottom of double-tube type reactor (8) are provided with products export, double-tube type reactor
(8) outer layer upper and lower ends have coolant liquid feed inlet and coolant liquid discharge port；
Raw material liquid supplying device (1) is delivered to the material liquid feed inlet of double-tube type reactor through feedstock transportation pipeline, for
Liquid charging stock is provided in double-tube type reactor；
Gas feed unit is delivered to the gas feed mouth of double-tube type reactor (8) through gas transfer pipeline (6), is used for double
Gas needed for reacting is provided in layer tubular reactor (8)；
Cooling device (25) is connect with the coolant liquid feed inlet of double-tube type reactor (8) and coolant liquid discharge port respectively, is used for
Coolant liquid is provided into the interlayer of double-tube type reactor (8)；
Product separator (12) is connect with the outlet for product of double-tube type reactor (8), for collecting the crude product after reacting；
Ammonia discharge port is provided at the top of product separator (12), the gas in crude product is delivered to bilayer through gas circulation line (15)
The recyclegas feed inlet of tubular reactor (8)；The side of product separator (12) is provided with by-product discharge port, and discharge outlet is set
Have sieve plate (30), the inside of product separator (12) is equipped with spiral conveyor rod (29), and the bottom of spiral conveyor rod (29) is equipped with filter
Plate (31)；Crude product is delivered to by-product discharge port by spiral conveyor rod (29), and the solid in crude product is squeezed into through sieve plate (30)
The bottom of byproduct collection device (13), product separator (12) is provided with outlet for product；Liquid in crude product is through filter plate
(31) it is exported after filtering out and being flowed out by outlet for product through product transfer pipeline (18), fluid sample is acquired by acquisition port, is met
It is required that being then delivered to fractionating device, it is then delivered to recycle feed liquid feed inlet if it does not meet the requirements；
The top of product fractionating device (19) is equipped with solvent discharge port, and the bottom of product fractionating device (19) goes out equipped with polysilazane
Material mouth, after the liquid fractionation in crude product, solvent is flowed out by solvent discharge port and is received through cooling tube (20) cooling solvent that is delivered to
Acquisition means (21)；Polysilazane is delivered to polysilazane collection device (22) after being flowed out by polysilazane discharge port；
The gas circulating tube road of described device is equipped with emptying pipeline (32), for emptying the air in double-tube type reactor.
3. a kind of preparation facilities of polysilazane as claimed in claim 2, it is characterised in that: on the transfer pipeline of described device
Equipped with valve, delivery pump, flowmeter, temperature sensor and temperature detector (9), delivery pump, flowmeter, temperature sensor and control
Device (28) processed connection, the delivery pump include material liquid delivery pump (2) on material liquid transfer pipeline (26), circulation ammonia delivery pipe
The product delivery pump (16) on circulation ammonia delivery pump (14) and product transfer pipeline (18) on road (15), the flowmeter include
The fluid flowmeter (5) and gas flowmeter (23) being set on pipeline；The valve includes the check-valves being set on pipeline
(3), shut-off valve (4) and pressure reducing valve (27)；The junction of the double-tube type reactor (8) and product separator (12) is equipped with thick
Products export valve (11)；Pressure is respectively equipped at the top of the top of the double-tube type reactor (8) and product separator (12)
Sensor and relief valve assembly (24).
4. a kind of preparation facilities of polysilazane as claimed in claim 2, it is characterised in that: the double-tube type reactor
(8) multilayer circular ring type isocon (7) is equipped in top interlayer, the both ends of isocon (7) are provided with isocon feed inlet respectively
(61) and isocon recycle feed mouth (62), isocon feed inlet (61) and the material liquid on double-tube type reactor (8) top into
Material mouth connection, isocon recycle feed mouth (62) are connect with the recycle feed liquid feed inlet on double-tube type reactor (8) top, often
Multiple isocon feed inlets are provided on layer isocon (7), the internal layer of double-tube type reactor (8) is provided with multiple and isocon and feeds
The connector of mouth connection.
5. a kind of preparation facilities of polysilazane as claimed in claim 4, it is characterised in that: the isocon (7) is level
Three layers of circular ring type structure being arranged, are uniformly provided with 4~16 upper layer isocon feed inlets (63) on the annulus of upper layer, on the annulus of middle layer
4~16 middle layer isocon feed inlets (64) uniformly are provided with, 4~16 lower layer's isocon feed inlets are uniformly provided on lower layer's annulus
(65), horizontal plane is divided into 12~48 equal parts by feed inlet interval on three layers of annulus.
6. a kind of preparation facilities of polysilazane as claimed in claim 2, it is characterised in that: filter plate (31) structure includes
Two layers of porous hard steel plate and 10~30 layers of cotton fibre or non-woven fabrics being clipped between steel plate.
7. a kind of preparation facilities of polysilazane as described in claim 1, it is characterised in that: the double-tube type reactor
(8) internal diameter is 100~1000mm, and it is highly 1000mm~5000mm that outer diameter, which is 140mm~1200mm,.
8. a kind of method for preparing polysilazane using such as claim 1~7 described device, it is characterised in that: the method step
It is rapid as follows:
Step S1: from gas feed unit in double-tube type reactor (8) supplying nitrogen, device is purged, device is made
Under nitrogen environment；
Step S2: -20~-35 DEG C of coolant liquid is conveyed into the interlayer of double-tube type reactor (8) from cooling device (25)；
Step S3: dimethyldichlorosilane is mixed with solvent according to the volume ratio of 1:1~50, raw material liquid supplying device (1) is added
In, and it is delivered to the top of double-tube type reactor (8), while defeated in double-tube type reactor (8) from gas feed unit
Send ammonia；The flow velocity of ammonia and material liquid is controlled, reactor pressure is kept to maintain normal pressure, reaction temperature is made to be less than or equal to 5
℃；
Step S4: the crude product after reaction is flowed into product separator (12) by double-tube type reactor (8) bottom, by crude product
In unreacted ammonia recycle be delivered to the tops of double-tube type reactor (8), by the Solid Conveying and Melting in crude product to by-product
Collection device (13)；After liquid output in crude product, by the fluid sample in thief hatch (17) acquisition crude product, test sample
In polysilazane whether meet requirement, next step operation is carried out if meeting；Double-tube type is recycled to if not meeting
The top of reactor (8), repeats step S3, and the raw material flow velocity of control ammonia, ammonia recycle and circulating liquid keeps bimetallic tube
Formula reactor (8) interior pressure maintains normal pressure, and reaction temperature is made to be less than or equal to 5 DEG C；It is carried out in next step until meeting requirement
Operation；
Step S6: the liquid for meeting requirement is delivered in product fractionating device (19), after fractionation, by solvent collection device
(21) solvent is collected, the polysilazane for meeting requirement is collected by polysilazane collection device (22).
9. a kind of method of polysilazane as claimed in claim 8, it is characterised in that: the dimethyldichlorosilane and solvent
Volume ratio be 1:10~20.
10. a kind of method of polysilazane as claimed in claim 8 or 9, it is characterised in that: the solvent is n-hexane, ring
One or more of hexane, benzene, toluene, tetrahydrofuran and butyl ether.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112791686A (en) * | 2021-01-06 | 2021-05-14 | 李腾飞 | Preparation method of epoxy zinc-rich primer base material |
| US20210317272A1 (en) * | 2018-07-24 | 2021-10-14 | A/G Innovation Partners, Ltd. | A system and method for a semi-continuous process for producing polysilazanes |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140341794A1 (en) * | 2012-08-10 | 2014-11-20 | Evonik Industries Ag | Process for the coupled preparation of polysilazanes and trisilylamine |
| US20150023859A1 (en) * | 2011-12-16 | 2015-01-22 | Evonik Industries Ag | Production of trisilylamine from monochlorosilane and ammonia by use of inert solvent |
| CN104998598A (en) * | 2015-08-18 | 2015-10-28 | 李登仙 | Preparation device and preparation method for polysilazane |
| CN105358478A (en) * | 2013-05-27 | 2016-02-24 | 赢创德固赛有限公司 | Method for the coupled production of trisilylamine and polysilazanes having a molar mass of up to 500 g/mol |
| CN105777793A (en) * | 2016-04-06 | 2016-07-20 | 衢州信步化工科技有限公司 | Column-type continuous synthesis method for hexamethyl-disilazane |
| CN106883257A (en) * | 2017-01-19 | 2017-06-23 | 浙江硕而博化工有限公司 | Trim,ethylchlorosilane produces HMDS new technology |
| CN108676167A (en) * | 2018-04-03 | 2018-10-19 | 中国科学院化学研究所 | A kind of preparation facilities and method of polysilazane |
| CN109748932A (en) * | 2019-01-09 | 2019-05-14 | 浙江新化化工股份有限公司 | A kind of continuous synthesis method of hexamethyldisilazane |
-
2018
- 2018-12-29 CN CN201811641247.6A patent/CN109627446A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150023859A1 (en) * | 2011-12-16 | 2015-01-22 | Evonik Industries Ag | Production of trisilylamine from monochlorosilane and ammonia by use of inert solvent |
| US20140341794A1 (en) * | 2012-08-10 | 2014-11-20 | Evonik Industries Ag | Process for the coupled preparation of polysilazanes and trisilylamine |
| CN105358478A (en) * | 2013-05-27 | 2016-02-24 | 赢创德固赛有限公司 | Method for the coupled production of trisilylamine and polysilazanes having a molar mass of up to 500 g/mol |
| CN104998598A (en) * | 2015-08-18 | 2015-10-28 | 李登仙 | Preparation device and preparation method for polysilazane |
| CN105777793A (en) * | 2016-04-06 | 2016-07-20 | 衢州信步化工科技有限公司 | Column-type continuous synthesis method for hexamethyl-disilazane |
| CN106883257A (en) * | 2017-01-19 | 2017-06-23 | 浙江硕而博化工有限公司 | Trim,ethylchlorosilane produces HMDS new technology |
| CN108676167A (en) * | 2018-04-03 | 2018-10-19 | 中国科学院化学研究所 | A kind of preparation facilities and method of polysilazane |
| CN109748932A (en) * | 2019-01-09 | 2019-05-14 | 浙江新化化工股份有限公司 | A kind of continuous synthesis method of hexamethyldisilazane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210317272A1 (en) * | 2018-07-24 | 2021-10-14 | A/G Innovation Partners, Ltd. | A system and method for a semi-continuous process for producing polysilazanes |
| CN112791686A (en) * | 2021-01-06 | 2021-05-14 | 李腾飞 | Preparation method of epoxy zinc-rich primer base material |
| CN112791686B (en) * | 2021-01-06 | 2022-11-15 | 安徽汇利涂料科技有限公司 | Preparation method of epoxy zinc-rich primer base material |
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